Basic phosphoric acid esters



United States Patent BASIC PHOSPHORIC ACID ESTERS Karl Gaetzi and Paul Miiller, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application March 16, 1953, Serial No. 342,736

Claims priority, application Switzerland March 28, 1952 9 Claims. cum-247.1

This invention concerns new phosphoric acid esters with a basic ester component, of the general formula wherein:

2,736,726 Patented Feb. 28, 1956 with an alkali metal salt of a primary or secondary basic alcohol or mercaptan of the general formula:

wherein R1, R2, X, Am, Y and alkylene have the meanings given above, if necessary in an inert solvent and at a raised temperature. Also the free basic alcohols or mercaptans can be used in the presence of acid binding agents instead of alkali metal salts.

As starting materials in the processes described above, there can be used on the one hand for example: dimethyl-, diethyl-, di-isopropylor di-n-butyl-phosphoric acid ester, -thiophosphoric acid ester or -dithiophosphoric acid ester or the chlorides or bromides of these phosphoric acid diesters or thiophosphoric acid diesters (dialkoxyphosphoryl halides or dialkoxy-thiophosphoryl halides), and on the other hand for example, dimethy1amino-, diethylamino-, dibutylamino-, pyrrolidino-, piperidinoand morpholino-ethyl chloride or -ethyl bromide, fl-dimethlylamino-, fl-diethylamino-, fl-piperidino-, fi-morpho- 1ino-, 'y-dimethylamino-, 'y-diethylaminoand 'y-piperidinopropyl chloride, fl-dimethylamino-isopropyl chloride or dimethylaminoand diethylamino-ethanol, fi-dimethylamino-, S-diethylaminoand 'y-piperidino-propanol, B-dimethylamino-isopropanol, 6-dimethylamino-, fi-diethylaminoand e-piperidino-n-butanol.

It has now been found that these compounds have a with a halogen alkylamine of the general formula:

YalkyleneAm wherein R1, R2, X, Am and alkylene have the meanings given above, and Y represents chlorine or bromine. The alkali metal salts, including ammonium salts can be used as salts of the acid phosphoric acid esters.

It is of advantage to perform the reactions in the presence of an indifferent solvent, e. giin a low molecular aliphatic alcohol or ketone, in a carboxylic acid ester or a benzene hydrocarbon.

Generally, the most favourable reaction temperature lies between 20 and 100 and is dependent on the reaction components so this statement is not in any way a limitation.

Instead of reacting the salts of phosphoric acid diesters with the halogen alkylamines, also phosphoric acid diesters themselves can be used in the presence of acid binding agents such as, e. g. sodium or potassium carbonate, pyridine or dimethyl aniline. 3

A further way in which the new basic phosphoric acid esters can be produced consistsflin the reaction. of a phosphoric acid diester halide of the general formula:

Rr-O S The following examples illustrate the production of the new compounds. Parts are given as parts by weight and the relationship thereof to parts by volume is as that of grammes to cubic centimetres. The temperatures are given in degrees Centigrade.

Example 1 21 parts of the sodium salt of 0.0-diethyl-dithiophosphoric acid ester are dissolved in 200 parts by volume of anhydrous acetone, 14 parts of freshly distilled fi-diethylaminoethyl chloride are added and the reaction mixture is stirred first for 3 hours at room temperature and then boiled for 2 hours under reflux while stirring. Sodium chloride soon precipitates. Water is added, the solution is made alkaline to soda and is ethered out. The ether solution after being washed with water is evaporated and the residue is distilled. S-(B- diethylaminoethyl)- 0.0 diethyl dithiophosphoric acid ester boils under 0.2 mm pressure at IDS-109.

Example 2 S (fi-diethylamin'oethyl) 0.0 diethyl dithiophos phoric acid ester as described in example 1 is obtained in a similar manner if diethylaminoethyl mercaptan is used instead of dimethylamino-ethanol, and diethyl-(fi-diethylamino-butyl)-thiophosphoric acid ester is obtained if vS-dimethylamino-butanol is used instead of dimethylamino-ethanol.

The following esters can also be produced by one of the methods described:

Example 3 Dusting agent.l part of active ingredient, e. g. ,B-diethylaminoethyl-diethyl thiophosphoric acid ester, is homogeneously ground with 99 parts of a carrier such as, e. g. talcum. Also adhesive agents can be added if desired to improve the adhesive properties of the dust coating on the plant.

Example 4 Wettable powder.l0 parts of active ingredient, e. g. S-(B- dimethylaminoethyl)-0.0-diethyl dithiophosphoric acid ester, and 10 parts of solid pulverised residue of sulphite waste liquor are homogeneously ground with parts of carrier, e. g. chalk, kaolin, bentonite. Should the spraying agent be required to have a greater wetting effect, the residue of the sulphite waste liquor can be replaced by 5 parts of the sodium salt of dibutylnaphthalene sulphonic acid and 5 parts of blood albumin.

Example 5 Emulsi0n.20 parts of active ingredient, e. g. S-( S- dimethylami noethyl)-0.0-diethyl dithiophosphoric acid ester, are dissolved in 40 parts of solvent and mixed with 40 parts of emulgating agent. Mixtures of benzene, toluene, xylene, acetone, low aliphatic alcohols, petroleum distillates for example can serve as solvents. The emulgating agents can be anion active, cation active or non-ionogenic. As examples can be named sulphonates of fatty acid esters, the sulphonate of ricinoleic acid butyl ester, quaternary compounds or condensation products of ethylene oxide with alkyl phenols or fatty alcohols. The concentrates can he emulsified with water to form ready-for-use emulsions.

What we claim is:

1. A basic phosphoric acid ester corresponding to the formula:

R1O\ /S ii B2O X-alkylene-Am wherein R1 and R2 each represent a lower alkyl radical,

X represents a member selected from the group consisting of oxygen and sulphur,

Am represents a member selected from the group consisting of lower dialkylaxnino, alkylenirnino containing 4 to 5 carbon atoms and morpholino radicals, and

Alkylene represents an alkylene radical containing from 2 to 4 carbon atoms.

2. A basic phosphoric acid ester corresponding to the formula:

cam-o s lower alkyl C 2H5-0 S CH1.C HgN lower alkyl 3. A basic phosphoric acid ester corresponding to the formula:

CgH5-:Q\ s

)P lower alkyl (hm-o o-oH,oHlN

lower alkyl 4. A basic phosphoric acid ester corresponding to the formula:

c-lui=o s /P CH:

s-om-om-N 5. A basic phosphoric acid ester corresponding to the formula:

s-oH orrr-N H 6. A basic phosphoric acid ester corresponding to the formula:

CHrCz 7. A basic phosphoric acid ester corresponding to the formula:

8. An insecticidal and acaricidal composition comprising as active ingredient a basic phosphoric acid ester corresponding to the formula:

Rr- S Rz--0 X-alkylene-Am wherein R1 and R2 each represent a lower alkyl radical,

9. Process for combatting pests comprising exposing 10 the pests to a toxic quantity of a compound according to claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 15 2,494,283 Cassaday et a1. Jan. 10, 1950 2,570,503 Tawney Oct. 9, 1951 2,586,656

Hook et a1 Feb. 19, 1952 

1. A BASIC PHOSPHORIC ACID ESTER CORRESPONDING TO THE FORMULA: 